Chelation-Assisted Substrate-Controlled Asymmetric Lithiation-Allylboration of Chiral Carbamate 1,2,4-Butanetriol Acetonide
Abstract
:1. Introduction
2. Results and Discussion
2.1. Chemistry
Entry | EIX | Additive L2 | Yield a (%) | d.r. b 4a:4b | (conc., CH3OH) |
---|---|---|---|---|---|
I | PhCHO | TMEDA | 69 | 51:49 | nd c |
(−)-Sp | 74 | 98:2 | −17.4 (1.0) | ||
(+)-Sp surrogate | 53 | 20:80 | nd | ||
None | 84 | 98:2 | −17.2 (1.0) | ||
II | Me3SnCl | TMEDA | 80 | 53:43 | nd |
(−)-Sp | 75 | 97:3 | +13.0 (1.2) | ||
(+)-Sp surrogate | nd | nd | nd | ||
None | 78 | 98:2 | +11.3 (1.1) | ||
III | PhCOPh | TMEDA | 72 | 50:50 | nd |
(−)-Sp | 80 | 95:5 | +23.6 (1.0) | ||
(+)-Sp surrogate | 61 | 29:71 | nd | ||
None | 84 | 95:5 | +27.3 (1.5) |
Entry | R2 | R3 | Yield (%) | d.r. a 8:8a | (conc., CH3OH) |
---|---|---|---|---|---|
I | Me | Ph | 56 | 90:10 | +10.4 |
II | Me | Cy | 54 | 95:5 | −19.5 |
III | Me | Bu | 60 | 92:8 | +21.9 |
IV | Bu | Ph | 48 | 90:10 | −14.5 |
V | Bu | Cy | 52 | 94:6 | −18.4 |
3. Experimental Section
3.1. General Information
3.2. (S)-2-(2,2-Dimethyl-1,3-dioxolan-4-yl)ethyl Diisopropylcarbamate (1)
3.3. 9-((E)-Prop-1-enyl)-9-borabicyclo[3.3.1]nonane (5a)
3.4. B-(trans-1-Hexenyl)-9-borabicyclo(3,3,1)nonane (5b)
3.5. (R)-3-((S)-2,2-Dimethyl-1,3-dioxolan-4-yl)-1-hydroxy-1-phenylpropan-2-yl Diisopropylcarbamate (4a-I)
3.6. (R)-3-((S)-2,2-Dimethyl-1,3-dioxolan-4-yl)-1-hydroxy-1,1-diphenylpropan-2-yldiisopropyl-carbamate (4a-III)
3.7. (S)-2-((S)-2,2-Dimethyl-1,3-dioxolan-4-yl)-1-(trimethylstannyl)ethyl Diisopropylcarbamate (4a-II)
3.8. (1R,2R,Z)-5-((R)-2,2-Dimethyl-1,3-dioxalan-4-yl)-2-methyl-1-phenylpent-3-en-1-ol (8-I)
3.9. (1R,2R,Z)-1-Cyclohexyl-5-((R)-2,2-dimethyl-1,3-dioxalan-4-yl)-2-methylpent-3-en-1-ol (8-II).
3.10. (4R,5S,Z)-1-((R)-2,2-Dimethyl-1,3-dioxolan-4-yl)-4-methylnon-2-en-5-ol (8-III)
3.11. (1R,2R)-2-((Z)-3-((R)-2,2-Dimethyl-1,3-dioxolan-4-yl)prop-1-en-1-yl)-1-phenylhexan-1-ol (8-IV).
3.12. (1S,2R)-1-Cyclohexyl-2-((Z)-3-((R)-2,2-dimethyl-1,3-dioxolan-4-yl)prop-1-en-1-yl)hexan-1-ol (8-V)
4. Conclusions
Supplementary Materials
Acknowledgments
Author Contributions
Conflicts of Interest
References
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Mahmood, A.; Alkhathlan, H.Z.; Parvez, S.; Khan, M.; Shahzad, S.A. Chelation-Assisted Substrate-Controlled Asymmetric Lithiation-Allylboration of Chiral Carbamate 1,2,4-Butanetriol Acetonide. Molecules 2015, 20, 9890-9905. https://doi.org/10.3390/molecules20069890
Mahmood A, Alkhathlan HZ, Parvez S, Khan M, Shahzad SA. Chelation-Assisted Substrate-Controlled Asymmetric Lithiation-Allylboration of Chiral Carbamate 1,2,4-Butanetriol Acetonide. Molecules. 2015; 20(6):9890-9905. https://doi.org/10.3390/molecules20069890
Chicago/Turabian StyleMahmood, Adeem, Hamad Z. Alkhathlan, Saima Parvez, Merajuddin Khan, and Sohail A. Shahzad. 2015. "Chelation-Assisted Substrate-Controlled Asymmetric Lithiation-Allylboration of Chiral Carbamate 1,2,4-Butanetriol Acetonide" Molecules 20, no. 6: 9890-9905. https://doi.org/10.3390/molecules20069890